CN1164534C - Iron catalyst and its prepn and application - Google Patents
Iron catalyst and its prepn and application Download PDFInfo
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- CN1164534C CN1164534C CNB011205539A CN01120553A CN1164534C CN 1164534 C CN1164534 C CN 1164534C CN B011205539 A CNB011205539 A CN B011205539A CN 01120553 A CN01120553 A CN 01120553A CN 1164534 C CN1164534 C CN 1164534C
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Abstract
The present invention discloses an iron series catalyst in a structure (I), a preparation method thereof and applications thereof to ethene catalytic oligomerization. The preparation method comprises: 2, 6-diacetyl pyridine and 9-amino fluorene hydrochloride react at one step to obtain a ligand, and the ligand then reacts with ferrous salt in tetrahydrofuran to obtain the catalyst. The catalyst of the present invention has high catalytic activity up to 10<5>g ethene. Mol<-1>Fe. h<-1> in ethene catalytic oligomerization.
Description
Technical field:
The present invention relates to a kind of Fe-series catalyst and method for making thereof and its application in the catalyzed ethylene oligomerisation.
Background technology:
Linear alpha-alkene is at synthetic detergent, lubricating oil, softening agent and prepare aspects such as linear low density polyethylene resin as comonomer and bringing into play important effect.Present industrial main employing SHOP method (US Patent 3686351,1972 and US Patent 3676523,1972), Chevron technology and Amoco technology (Applied Homogeneous Catalysis with OrganometallicCompounds.Vol.1, VCH publishers, New York 1996:245-256) prepares linear alpha-alkene by ethylene oligomerization.The novel high-activity rear transition metal ethylene oligomerization catalyst (Organometallics, 1997, the 16:2005-2007 that grew up in recent years; J.Am.Chem.Soc., 1998,120:7143-7144) can prepare linear alpha-alkene by highly selective.In China, long-chain alpha-olefin has been realized self-sufficiency with the wax destructive distillation method, although and short chain alpha-olefin such as 1-hexene and 1-octene market demand are very big, the main dependence on import of present China.The design of effective catalyst is the gordian technique of ethylene oligomerization technological process, two selectivity that judgement criteria is catalyst activity and oligomerization product that it is important.
Summary of the invention:
The object of the present invention is to provide a kind of Fe-series catalyst and method for making thereof.
The present invention also aims to provide the application of a kind of Fe-series catalyst in the catalyzed ethylene oligomerisation, catalyzer of the present invention and methylaluminoxane are formed catalyst system, catalyzed ethylene oligomerisation.
A kind of Fe-series catalyst structure of the present invention is (I):
The preparation of a kind of Fe-series catalyst I of the present invention is with 2, and 6-diacetyl pyridine and 9-aminofluorene hydrochloride obtain part through single step reaction; React in tetrahydrofuran (THF) with ferrous salt then and obtain ethylene oligomerization catalyst.
The method for making of a kind of Fe-series catalyst I of the present invention in molar part, follows these steps to carry out:
1 under nitrogen protection, at first adds 20～100 parts of (preferred 40～80 parts) 9-aminofluorene hydrochlorides and 10 part 2 in reactor, and the 6-diacetyl pyridine injects methyl alcohol, stirs.Drip the formic acid or the Glacial acetic acid of 20～100 parts of triethylamines (preferably with 9-aminofluorene hydrochloride equivalent) and catalytic amount then, conventional purifying obtains part behind reaction 24～72h under 20～70 ℃.The concrete scheme of the purifying of crude product can be: with tetrahydrofuran (THF) dissolving, filter, filtrate precipitate in cold methanol obtained white solid then, and filtration, washing, drying, preservation is standby under nitrogen.
2 under nitrogen protection, and at first adding aforementioned proportion in reactor is the part and the FeCl of 1: 0.9～1.1 (being preferably 1: 0.95)
24H
2O.Inject tetrahydrofuran (THF) then, stir, behind reaction 2～4h under 20-60 ℃, filtration, washing, drying, specifically, after reaction finishes, add Skellysolve A, the gained throw out is filtered, with Skellysolve A, ether washing for several times, drying obtains the deep green solid catalyst, preserves standby under nitrogen.
The application of a kind of Fe-series catalyst of the present invention in the catalyzed ethylene oligomerisation, promotor are methylaluminoxane (MAO); Described Fe-series catalyst consumption is 10～400 μ mol/L, and the best is 40～200 μ mol/L; The Al/Fe mol ratio is 500～5000, and the best is 1000～4000; Temperature of reaction is-10 ℃～80 ℃, and the best is 20 ℃～60 ℃; Ethylene pressure is 0.1MPa～1.5MPa.
A kind of Fe-series catalyst of the present invention has following characteristics:
1. catalyzer of the present invention is that the pyridine diimine iron that fluorenyl replaces is ethylene oligomerization catalyst.
2. the catalytic activity height is generally 10
5G ethene mol
-1Feh
-1
3. when catalyzer of the present invention was used for ethylene oligomerization, product mainly concentrated on C
4～C
10Alkene, content is 74.3%～97.8%, linear C
4～C
10Alpha-olefin content is more than 98%.
Embodiment:
Embodiment 1.
1. Preparation of catalysts
Under nitrogen protection, at first in reactor, add 0.2000g (1.23mmol) 2,6-diacetyl pyridine and 1.0710g (4.92mmol) 9-aminofluorene hydrochloride injects 50mL methyl alcohol, starts stirring.Drip 0.4979g triethylamine and 0.2mL formic acid then, react 48h down at 40 ℃.Crude product dissolves, filters with tetrahydrofuran (THF), and precipitation obtains 0.3553g white solid (productive rate: 59.0%) in cold methanol then.
1HNMR(C
6D
4Cl
2，δppm)：7.99(d；Py-m-H)，7.7(t；Py-p-H)，7.35～6.9(m；-Ar-H-)，5.85(s；＞CH-)，2.92(s；CH
3C＝O)。
13CNMR(C
6D
4Cl
2，δppm)：193.04，144.54，134.55，129.08，128.00，124.29，122.8，120.25，14.32。EI-MS(70eV)：m/z＝489[M
+]，487[M
+-2H]。Ultimate analysis (%): calculated value: C 85.89, H 5.52, and N 8.59; Measured value: C 85.41, H 5.65, and N 8.60.
Under nitrogen protection, at first in reactor, add above-mentioned part of 0.21mmol and 0.20mmolFeCl
24H
2O starts stirring.Inject the 5mL tetrahydrofuran (THF) then, react 2h down at 25 ℃.After reaction finishes, add Skellysolve A, the gained throw out is filtered, with Skellysolve A, ether washing for several times, obtain 0.1038g deep green solid catalyst (productive rate: 84.2%).m/z＝616[M
+]，581[M
+-Cl]。Ultimate analysis (%): calculated value: C 68.20, H 4.42, and N 6.82; Measured value: C 67.97, H 4.68, and N 6.91.
2. ethylene oligomerization
Exsiccant 250mL three-necked bottle is vacuumized, replaces repeatedly with argon gas, and with the ethene displacement once, the maintenance pressure of the inside of a bottle is 770mmHg.Oil bath is warming up to 40 ℃.
Inject the toluene of 50mL with syringe, start stirring through dehydration and deoxidation.Inject promotor methylaluminoxane 1.43mL with syringe earlier, stir 5min, add 4 μ mol catalyzer then.The AL/Fe ratio is 500.
Reaction 30min adds 10% ethanol solution hydrochloride termination reaction.Operational condition and oligomerisation data are listed in the table 1.
Embodiment 2.
1. Preparation of catalysts
2. ethylene oligomerization
The AL/Fe ratio is 1000.Other condition is with embodiment 1.
Embodiment 3.
1. Preparation of catalysts
With embodiment 1.
2. ethylene oligomerization
The Al/Fe ratio is 2000.Other condition is with embodiment 1.
Embodiment 4.
1. Preparation of catalysts
With embodiment 1.
2. ethylene oligomerization
The Al/Fe ratio is 3000.Other condition is with embodiment 1.
Embodiment 5.
1. Preparation of catalysts
With embodiment 1.
2. ethylene oligomerization
Temperature of reaction is 20 ℃.Other condition is with embodiment 1.
Embodiment 6.
1. Preparation of catalysts
With embodiment 1.
2. vinyl polymerization
Temperature of reaction is 60 ℃.Other condition is with embodiment 1.
Embodiment 7.
1. Preparation of catalysts
Under nitrogen protection, at first in reactor, add 0.2000g (1.23mmol) 2,6-diacetyl pyridine and 2.1420g (9.84mmol) 9-aminofluorene hydrochloride injects 50mL methyl alcohol, starts stirring.Drip 2.1420g triethylamine and 0.2mL Glacial acetic acid then, react 48h down at 50 ℃.Crude product dissolves, filters with tetrahydrofuran (THF), and precipitation obtains 0.3926g white solid (productive rate: 65.2%) in cold methanol then.
Under nitrogen protection, at first in reactor, add above-mentioned part of 0.21mmol and 0.20mmolFeCl
24H
2O starts stirring.Inject the 5mL tetrahydrofuran (THF) then, react 4h down at 25 ℃.After reaction finishes, add Skellysolve A, the gained throw out is filtered, with Skellysolve A, ether washing for several times, obtain 0.1081 deep green solid catalyst.(productive rate: 87.7%)
2. ethylene oligomerization
The autoclave of 500mL is heated to 200 ℃ and vacuumized 2 hours, charge into ethene through nitrogen replacement for several times, cool to preset temperature, add 100mL toluene and 11.43mLMAO successively, stir and add 8 μ mol catalyzer (the Al/Fe ratio is 2000) after 2 minutes rapidly, under 40 ℃ and 0.3Mpa ethylene pressure, carry out oligomerisation reaction, behind the reaction 30min with ice bath cooling, release, with 10% acidifying ethanol termination reaction.
Embodiment 8.
1. Preparation of catalysts
With embodiment 7.
2. ethylene oligomerization
Ethylene pressure is 1.0MPa.Other condition is with embodiment 7.
Embodiment 9.
1. Preparation of catalysts
With embodiment 7.
2. ethylene oligomerization
Ethylene pressure is 1.5MPa.Other condition is with embodiment 7.
Reaction conditions among table 1. embodiment and oligomerisation data
a
Product carbon number distribution (%)
Temperature of reaction ethylene pressure Al/Fe ratio
Embodiment oligomerisation activity
bLinear C
4-10
(℃) (MPa) (mol/mol) C
4-10
Alpha-olefin
Embodiment 1 40 0.1 500 0.37 84.3 99.6
Embodiment 2 40 0.1 1,000 0.51 94.7 99.4
Embodiment 3 40 0.1 2,000 0.66 96.9 98.8
Embodiment 4 40 0.1 3,000 0.75 97.8 98.5
Embodiment 5 20 0.1 2,000 0.96 92.2 99.7
Embodiment 6 60 0.1 2,000 0.55 97.6 98.6
Embodiment 7 40 0.3 2,000 1.85 86.4 98.1
Embodiment 8 40 1.0 2,000 2.96 75.4 98.7
Embodiment 9 40 1.5 2,000 4.21 74.3 98.5
aCatalyst concn is 80 μ mol/L.
bActivity unit is 10
6G ethene mol
-1Feh
-1
Claims (8)
1. Fe-series catalyst, its structure is (I):
2. the method for making of a kind of Fe-series catalyst of claim 1 in molar part, follows these steps to carry out:
1. under nitrogen protection, at first in reactor, add 20～100 parts of 9-aminofluorene hydrochlorides and 10 part 2, the 6-diacetyl pyridine injects methyl alcohol, stirs; Drip the formic acid or the Glacial acetic acid of 20～100 parts of triethylamines and catalytic amount then,, with the tetrahydrofuran (THF) dissolving, filter, filtrate is precipitated in cold methanol obtained white solid then at 20～70 ℃ down behind reaction 24～72h;
2. under nitrogen protection, at first in reactor, add aforementioned proportion and be 1: 0.9～1.1 part and FeCl
24H
2O; Inject tetrahydrofuran (THF) then, stir, behind reaction 2～4h under 20-60 ℃, add Skellysolve A, the gained throw out is filtered, wash for several times with Skellysolve A, ether, drying obtains the deep green solid catalyst.
3. according to the method for making of claim 2, it is characterized in that: in step 1, described 9-aminofluorene hydrochloride is 40～80 parts.
4. according to the method for making of claim 2, it is characterized in that: in step 1, described triethylamine and 9-aminofluorene hydrochloride equivalent.
5. according to the method for making of claim 2, it is characterized in that: in step 2, described part and FeCl
24H
2The O consumption is 1: 0.95.
6. the application of a kind of Fe-series catalyst in the catalyzed ethylene oligomerisation of claim 1.
7. according to the application of claim 6, it is characterized in that: promotor is a methylaluminoxane; Described Fe-series catalyst consumption is 10～400 μ mol/L; The Al/Fe mol ratio is 500～5000; Temperature of reaction is-10 ℃～80 ℃; Ethylene pressure is 0.1MPa～1.5MPa.
8. according to the application of claim 6, it is characterized in that: described Fe-series catalyst consumption is 40～200 μ mol/L; The Al/Fe mol ratio is 1000～4000; Temperature of reaction is 20 ℃～60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011205539A CN1164534C (en) | 2001-07-20 | 2001-07-20 | Iron catalyst and its prepn and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011205539A CN1164534C (en) | 2001-07-20 | 2001-07-20 | Iron catalyst and its prepn and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1398836A CN1398836A (en) | 2003-02-26 |
| CN1164534C true CN1164534C (en) | 2004-09-01 |
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ID=4664230
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011205539A Expired - Fee Related CN1164534C (en) | 2001-07-20 | 2001-07-20 | Iron catalyst and its prepn and application |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050085108A (en) * | 2002-11-21 | 2005-08-29 | 피나 테크놀러지, 인코포레이티드 | New catalyst structure for olefin polymerization |
| CN105268480B (en) * | 2015-10-19 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of method of the hexene of ethylene oligomerization coproduction 1 and 1 octene of corrdination type catalyst and the use catalyst |
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2001
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